Azodyestuff and process of making same



Patented Aug. 21, 1934 UNITED STATES FYFICE PA NT 1,970,661- AZODYESTUFF AND PROCESS F .MAKING SAME . Leopold Laska and Arthur Zitscher, Oifenbachon-the-Main, Germany, assignors to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application August l, 1930, Serial No. 472,483. In Germany September 26, 1929 Claims. (01. 260-97) wherein the benzene nucleus signified by I and the aryl-radical may be substituted, only such components being used as do not contain any group rendering the dyestuffs soluble in water and alkalies, such as the 'sulfonic or carboxylic acid group. 1

The combining components used inthis process may be produced in the manner described in U. S. Patent No. 1,868,612.

The new dyestuffs may be produced in substance, or on a fillerin order to prepare color lakes. They are of an especial importance for the production of ice colors. They yield when produced on the fiber brown shades which are of a particular value for the batic industry because of the beauty and brightness of these shades. According to the diazo-compounds used, the shades vary from the different brownsto brownish black and black. The arylamides used by the present process show so great an afiinity to the vegetable and animal fiber, that the goods padded therewith may be developed with diazo-compounds without being previously dried.

In order to further illustrate our invention the following examples are given, the parts being by weight and all temperatures in centigrade degrees, but it is however to be understood, that our invention is not limited to the particular products or the reaction conditions mentioned therein.

Example- 1 Well boiled and dried cotton yarn is impregnated with a solution containing per liter 20 grs. of '3-hydroXy-diphenylaminel-carboxylic acid anilide, cc. of caustic soda solution of 34 Be.

and 20 cc. of Turkey red oil. Then it is well wrung obtained. {Ihe dyestuff' thus produced-on, the fiber corresponds to the. iormula:

Gaga-NE Example 2 OH OCH;

mQ aGWEG I Example 3 In order to'impregnate cotton with hydroxydiaryl-amine-carboxylic acid aryl-amides in a bath containing sodium chloride, one may work as follows:

4 grs. of the para-nitroariilide of 3-hydroxy- 4.-chloro-diphenylamine-4carboxylic acid, 10 cc/bi' Turkey red oil of 50% strength and 8 cc. of a caustic'soda solution of 34 B. are made to a paste. This paste is warmed slightly a'nddise solved while boiling with the addition of 20cc. of hot soft water. By the admixture of cold water the mass is made up to '1000 cc. and then mixed with 10 grs. of common salt. In this solution the material to be dyed is impregnated at 30"for 30 mirutes. Then the paddedand dehydrated material is developed by agitating it for half an hour in a diazo solution.

Example 4 Cotton yarn previously treated'in the appropriate manner is impregnated in a solution containing per liter 15 grs. of the beta-naphthylamide of 3-hydroxy-diphenylaminel-carboxylic acid, 30 cc. of caustic soda solution of 34 B. and 10 cc. of Turkey red oil. Then the goods are well wrung out and developed in a diazo solution neutralized with. sodium-bicarbonate and corresponding per liter 1 to 1.28 grs. of 3- chloro-aniline. Then they are rinsed and soaped at the boil.

In this manner a full dark brown dyeing is obtained. The dyestufl thus produced on the fiber corresponds to the formula:

V t. Example 5 Well boiled and dried cotton yarn is impregnated with a solution containing per liter 10 grs. of the dianisidide of 3-hydroXy-diphenylamine--carboxylic acid, 15 cc. of caustic soda solution of 34 B. and 10 cc.Turkey red oil. Then it is dehydrated well and developed with the A diazo solution neutralized with sodium acetate and containing per liter 1.52 grs. of 5-nitro-2- amino-l-methyl-benzene. It is then rinsed andsoaped at the boil. In this manner a dark brown dyeing is obtained. The dyestuff thus produced on the fiber corresponds to the formula:

is made up to 1 liter liquor.

- Q Degummed spun silk is padded in, this solution, squeezed offand developed with the diazo-solurtion neutralized with sodium acetate and containing per liter 1.62 grs. of 2.5-dichloro-aniline with the addition of a small amount of acetic acid. After rinsing, acidifying and hot soaping a full yellowish brown dyeing is obtained. The dyestuff thus produced on the fiber corresponds to the formula:

By starting with the para-nitranilide of 3- hydroxy 4' chloro diphenylamine 4 car boxylic acid and with the same diazo-compound a dark yellowish brown dyeing is obtained, While with the 2.5-dichloro-anilide an olive-brown dyeing is obtained. Whenthe diazo-compound is replaced by diazotized Q-amino-azo-benzene and the same arylamides are used, claret red shades are obtained.

Example 7 Viscose silk is padded with the solution containing per liter 3 grs. of the para-nitranilide of 3 hydroxy 4'-chloro-diphenylamine-4-carboxylic acid, 4.5 cc. of caustic soda solution of 34 B. and 3 cc. of Turkey red oil; Then the material is squeezed off and developed with the diazo-solution neutralized with sodium acetate and containing per liter 2 grs. of l-amino-azobenzene. After working up in the usual maner a dark violet-red dyeing is obtained. The dyestuif thus produced on the fiber corresponds to the formula:

In the same manner a claret red dyeing is obtained by replacing the para-nitranilide by the corresponding ortho-anisidide.

Example 8 Acetate silk is impregnated with the solution containing per liter 0.5 gr. of 4-amino-azo-benzene and 1 cc. of hydrochloric acid of,20 B. After rinsing the material is treated in the customary manner in the bath of nitrite and hydrochloric acid. Then it is again rinsed and developed in a solution containing per liter 2 grs. of the ortho-anisidide of 3-hydroxy-4-chlorodiphenylamine 4-carboxylic acid and 2 cc. of caustic soda solution of 34 B. In this manner a full red dyeing is obtained. The dyestuff thus produced on the fiber corresponds to the formula:

By replacing the ortho-anisidide by the corresponding 2-5-dichloro-anilide and working otherwise in-the same way a brown dyeing is obtained.

Example 9 Wool is impregnated with the solution containing per liter 3 grs. of the 2.5-dichloro-anilide of 3-hydroxy-4'-chloro diphenylaminei-carboxy I I he acid 4.5 cc of Caustic: soda Solution of 0 B' Diazocompound of Oomblmng component Shade obtalned 3 cc. of Turkey red oil and 50 grs. of common salt. The material is well squeezed and developed with g g i t z g blackish 8 m the diazo-solution neutralized with sodium-acey enzene 3,.;;?5.,,5;2fg car my F 80 t t d t i i per lit L62 grs. f 25.. 2-nitro-aniline; 3-hydroxy-4'-phenoxy-di- Yellowish brown.

phenylamine-4-carboxyldlchloro-anihne. Thereafter it is rinsed and macid.pam nitm.am1ide, soaped as usual. In this manner a brown dye- Z' 1 & Black- 7 0x -amn -a mg'isobtamed. The dyestuff thus produced on g 1 M0 3,333,5 5, 5 OXY n th fib corresponds t th f l 4-amino-3.2-d1meth- 3-hydroxy-2-methy1-5- Reddishbrown. 8,5

' yl-azo-benzenc. chloro-diphenylaminei- O H 01 carboxylic-acid para-nitro-anilide.

, 1 benzoylamino 4 3 -hydroxy- 3' -methyl -4 Violet-brown. g NH. ammo 2.5 diethchloro-diphenyl amineoxy-benzenc. 41;]carbozxy1ict-h acid g5- C1 0 010- -me oxy-p 8- i 1 1 nyl) -amide. (9U) l-amino-anthraquin- 3 hydroxy 3 methyl 4- Brown. N:N one. methoxy diphenylamine-4-carboxylic-acidpara-nitro-anilido.

01 v The following table shows the shades of some Since an object of the present invention is to other dyestuffs of this series: provide dyestuffs of good. fastness properties,

which dyestuffs are insoluble in water and alka- Diazocompound of Combining component Shade obtained 1t 15 to be understood that j aromatlc numel of the general formula appearing 11). the appended claims do not contain any substituents which are 11m '1' ls-11d -4-hl -d'- alchmoamme .Z Bmwn known to render organic compounds soluble in y acideorthotoluididewater or alkalies and to tend to depreciate the -2- a-ndi -4-11 -d'- d'- i 4 filt at -at??? Z f$nnei3 3 Re bmwn fastness of the dyestuffs to alkalies. substituents 1 bemoyhmmo gg-ggg; fggzg i g gn D0 of this kind are, for instance, the sulionic acid and amino-5.5mmplienylszlmine-i-caribgxthe cerboxylic d group this oxy-benzene- Y ic-flci r i The structural formulae given for our new azobl r iline 3 h drox -'4-chloro-di- Yellowlshb n. 2 5 0 an i phgnyllgmineamrbok r dyestufis are correct to the best of our knowledge a gig;- pamphenetlc and belief. However, it has not yet been possible 1. Brown to definitely determine the exact structure of g gg i n g g g these new a-zo-dyestuffs. For example, it is conw gf p p ceivable that the azo group is attached toithe 4-amino ll-megh- 3-hgdro1xy-4 -chl2ro-di- Reddish brown. phenyl nucleus II in ortho-position to the hyi 16H en -am1ne- -(31X' 323 I y goxyfleacidmawchlow droxyl group instead of 111 para-posit1on as indianilide. cated in the structural formula given 'Conse '1' -hd -4'-h1 -d'- 1 h (110mm 3 ii en y i amin car Yelowls brown quently we wish it understood that when such 15 g g aeid para I structural formulae are employed in the appended Reddish brown claims, they are intended to define the new azod i men ec i er, Darklet dyestuiifs which we have described and which may i f be obtained in accordance with our disclosure. Meta dichloro Reddishbrown. We claim: 6 g benzidine. a Brown 1. Process which comprises combining an aro- 321518.; m 0 am 7 Y 11 brown matic diazo compound of the benzene or anthra- 9 quinone series, with a 3-hydroXy-diphenylamine- 4' nitro 2.5 di 3- y yf oro- Vio et-b ac v l-carboxylic-acid-aryl-amide of the formula:

methoxy -4 ami phenyl amine 4 car V f no-azo-bcnzene boxylic acid (4 OH 7 25 chloro 2 methoxy t a l d 111 4 a il i hl 6 Y 11 hb V i 2.5 ic or'o y roxyoroie owis rown.

amino-l-toluene. phenyl amine -4 car I NH C0-NH.R

boxylic acid -ace11aph thyl-amide 4-ch1oro-2-amino- 3-hydroxy-4 -chloro-di- Brown. 7 wherein R stands for a radical of a mono-nuclear we diphenyl-etherfix ng-2 3 39;? :5: V V or polynuclear isocyclic aromatic compound and thraquinonyl-amide. wherein the benzene nucleus signified by I may 2 -chl0ro -4-nitro Bis (3 hydroxy 4' Deep brown. f

aniline (2 molecw 0mm diphenyl um be substituted by alkyl, alko: y, ary-o y or halogen. m proportions) in? 4 carboxylic 2. Process which comprises combining an arcgg g g 0% a g y matic diazo compound of the benzene series which M, e IX; f 4-chloro- 1Z-amincz- Bishl- (a -dhygrox31 4' Yellowish brown. may be substltuted y l, xy, ryl xy,

dipheny -ether 2 0 etc ip eny am a m molecular proporine-4-carboxylicacid)- yla arylamln? nltlo groups 0r 1131.0 gen tions). (2.5 dichloro phenyl) atoms, or a further diazo or an azo group, with a 1.4-diamide. v -h ro h. 1' e- 5 -nitro-2-amin0- -3-hydroxy-2-chloro-di- Reddishbrown. 3 yd F W 4 carboxyhc acid 1 methoxy ben Imam. mine. 4 car alYl-Etflllde of the foimula. zcne. boxylic acid ortho I V anisidide. U OH 1 amino anthra 3 iihylgiroxy 4 methyl Fgll r eddish quinone. ip eny -amine-4-csrrown.

boxylic acid ortho M @NH I I Q0.NH@ anisidide.

, 2.4,5- trichloro -ani- 3 hydroxy 2; methyl Yellowish brown. I p a gggfi i-gga figg wherein the benzene'nucleus I may be substituted naphthglidg, by alkyl, a1kcxy,.aryloxy or halogen and the ben- "3 zene nucleus III may be substituted by nitroalkyl phenylamme-4-carboxylv r l icacid-betanaphthalide. alkoxy, aryloxyor a n. gg' g gg g zi ?gg g Reddlshbrqwn- 3. Process which comprises combining an aroi ci nmd matic diazo compoundof the benzene series which T1501 may contain alkyl, alkoxy, aryloxy or nitroogen or nitro, with a 3-hydroXy-diphenylamine4- carboxylic acid arylamide of the formula:

wherein X stands for alkyl, alkoxy or halogen andwherein the benzene nucleus 'III may be substituted by alkyl, alkoxy, aryloxy, halogen or nitro.

5. Process which comprises combining an arcmatic diazo-compound of the benzene series which groups or halogen-atoms, with a 4f-chloro-3- hydroXy-diphenyL-amine 4 carboxylic acid-nitranilide of the formula:

on I

6. Process which comprises combining an arcmatic diazo-compound of the benzene series which i may contain alkyl, alkoxy, aryloxy or nitrogroups or halogen-atoms, with a 4-chloro-3- hydroxy diphenyl amine 4 carboxylic acidpara-nitranilide of the formula:

'7. Process which comprises combining the diazocompound of 2-5-dichloro-aniline with lchloro-3-hydroXy-dipheny1 amine--carboxylicacid-para-nitranilide of the formula:

8. The 'azo dyestuffs which are obtainable by combining an aromatic diazo compound of the benzene or anthraquinone series with a 3-hydroxydiphenylamine carboxylic acid-arylamide of the formula:

wherein R stands for a radical of a mononuclear or polynuclear isocyclic aromatic compound, and

wherein the benzene nucleus signified by I may be substituted by alkyl, alkoxy, aryloxy or halogen.

9. The azo dyestuffs of the general formula:

wherein the benzene nucleus I may besubstituted by alkyl, alkoxy, aryloxy or halogen, the benzene nucleus III may be substituted by nitro, alkyl,

1,970,661: may be substituted by alkyl, 'alkoxy, aryloxy,ha1-

alkoxy, aryloxy or halogen, and the benzene nucleus IV may be substituted by alkyl, alkoxy,

' aryloxy, acylamino, arylamino, nitro groups or halogen atoms ora further diazo or an azo group.

10. The azo-dyestufis of the general formula:

wherein X means alkyl, alkoxy or halogen and the nuclei III and. IV may be substituted by alkyl, alkoxy, aryloxy, halogen or nitro, which com- 1 pounds yield when produced on a substratum brown shades.

11. The azo-dyestuffs of the general formula:

wherein the nuclei III andiIV may be substituted by alkyl, alkoxy, aryloxy, halogen or nitro, which compounds yield when produced on a substratum brown shades.

12. The azo-dyestulfs of the general formula:

wherein the nucleus IV may be substituted by alkyl, alkoxy, aryloxy, halogen or nitro, which compounds yield when produced on a substratum brown shades. r

13, The azo -dyestuffs of the general formula:

. OH G G Q wherein the nucleus IV may be substituted by alkyl, alkoxy', aryloxy, halogen or nitro,- which compounds yield when produced on a substratum brown shades. 14. The azo-dyestuff of the formula:

whichcompound yields when produced on a substratum yellowish brown shades.-

15. The azordyestufi? of the formula:.

- I-w c] which compound yields when produced on a substratum brown shades.

16. The azo-dyestufi of the formula:

OH 0 CH3 i O N which compound yields when produced on a substratum full reddish-brown shades.

17. Fiber dyed by means of the azodyestuffs claimed in claim 8.

of the of the azodyestuffs of the azodyestuffs of the azodyestuffs of the azodyestufis LEOPOLD LASKA. ARTHUR ZITSCHER. 

